CN103582690A - Preparation methods of core-shell nanoparticles and solution thereof - Google Patents

Preparation methods of core-shell nanoparticles and solution thereof Download PDF

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CN103582690A
CN103582690A CN201180070699.3A CN201180070699A CN103582690A CN 103582690 A CN103582690 A CN 103582690A CN 201180070699 A CN201180070699 A CN 201180070699A CN 103582690 A CN103582690 A CN 103582690A
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shell
core
solution
preparation
mercaptan
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CN103582690B (en
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付敏
刘涛
韩德滋
卢华昌
马熠龙
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Bayer China Ltd
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Clariant International Ltd
Bayer Technology and Engineering Shanghai Co Ltd
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    • C09K11/56—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing sulfur
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    • C30B29/00—Single crystals or homogeneous polycrystalline material with defined structure characterised by the material or by their shape
    • C30B29/10—Inorganic compounds or compositions
    • C30B29/46—Sulfur-, selenium- or tellurium-containing compounds
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    • C30B29/00—Single crystals or homogeneous polycrystalline material with defined structure characterised by the material or by their shape
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    • H01L31/04—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof adapted as photovoltaic [PV] conversion devices
    • H01L31/054—Optical elements directly associated or integrated with the PV cell, e.g. light-reflecting means or light-concentrating means
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    • Y02E10/50—Photovoltaic [PV] energy
    • Y02E10/52—PV systems with concentrators

Abstract

Provided are preparation methods of core-shell nanoparticles and solution thereof. The preparation method of a core-shell nanoparticle solution comprises the following steps: adjusting the temperature of a semiconductive nanoparticle solution to a presetting shell layer encapsulating temperature; adding the shell layer precursor solution to the semiconductive nanoparticle solution, and reacting at the presetting shell layer encapsulating temperature, wherein the shell layer precursor solution is formed by mixing zinc salt, alkyl thiol and nonpolar organic solvent; and obtaining the core-shell nanoparticle solution after the reaction carries on for a period of presetting reacting time. The core-shell nanoparticles have the merits of high fluorescence quantum yield, nontoxic, low production cost, and simple process.

Description

Preparation methods of core-shell nanoparticles and solution thereof
A kind of method and technology field for preparing core-shell nano and its solution
The present invention relates to a kind of method for preparing core-shell nano and its solution.Background technology
Inorganic semiconductor nanoparticle has that performance stabilization, exciting light spectrum width, fluorescence spectrum be narrow, luminescent properties by surrounding environment influence it is small the features such as, luminous organic material can be effectively replaced, is widely used in fields such as solar cell, light emitting diode, fluorescence probe, biomarker, anti-fake mark, function film, laser, electronic communications.
Most of inorganic semiconductor nanoparticles to environment due to that containing elements such as cadmium, arsenic, lead, selenium, with compared with high toxicity, can pollute, be unfavorable for commercial applications.Thus, the semi-conductor nano particles that nontoxic or low toxicity, the sun absorption coefficient of light are high, photostability is high have obtained extensive research, such as IB-IIIA-VIA races nano-particle or IIB-IB-IIIA-VIA races nano-particle.
However, plane of crystal defect and accessory substance that these semi-conductor nano particles are produced in preparation process, can all turn into fluorescent quenching center, and reduce the fluorescence quantum yield of semi-conductor nano particles.Research is found, semi-conductor nano particles are wrapped up using the inorganic semiconductor material of broad stopband to form a kind of core-shell nano, the defect of plane of crystal can be effectively reduced, the fluorescence quantum yield of semi-conductor nano particles is improved, strengthens photostability.
Generally, the technique wrapped up semi-conductor nano particles is at a certain temperature, will to be slowly added dropwise or inject in semi-conductor nano particles solution for the shell precursor solution for forming shell, carries out encapsulation reaction.Shell precursor solution can be mixed to form by metal salt, sulphur source, organic coordination compound and solvent etc..The selection of sulphur source, the selection of organic coordination compound and concentration, shell parcel temperature, shell encapsulation reaction time and dropwise addition mode have considerable influence to the luminescent properties of core-shell nano, particle size, pattern, crystal structure.
Oneself has been reported that description zinc sulphide（ZnS) the technique that shell precursor solution is wrapped up on semi-conductor nano particles surface, it is intended to improve the fluorescence quantum yield of semi-conductor nano particles.For example, Renguo Xie etc. use zinc stearate as zinc salt, sulphur powder is matched somebody with somebody as sulphur source, oleyl amine as organic Compound, CuInS has been synthesized at 180 °C2/ ZnS core core/shell nanoparticles.The fluorescence quantum yield of the nano-particle can reach 30%.They are also prepared for AgInS using identical method2/ ZnS core core/shell nanoparticles (Renguo Xie, et al., JACS, 2009,131,5691-5697).
And for example, Thomas Pons etc. are used as organic coordination compound, the C of synthesis as zinc salt, double hexyl zinc dithiocarbamates using zinc stearate as sulphur source, tri octyl phosphine and oleyl amineUInS2/ ZnS core-shell nano fluorescence quantum yield highests can reach 30% (Thomas Pons, et al., ACS Nano, 2010,4 (5), 2531-2538).
For another example, using zinc stearate as zinc salt, xanthopone as sulphur source in the mixed liquor for being dissolved in octadecylene, dimethylformamide and toluene, and CuInS is added dropwise in above-mentioned mixed solution by Liang Li etc.2In nano-particle solution, CuInS is obtained2/ ZnS core core/shell nanoparticles（Liang Li, et al " Chem. Mater. 2009,21,2422-2429), its fluorescence quantum yield can reach 60%, be CuInS210 times of nano-particle.
Further, Victor I. Klimov seminars are using zinc stearate or cadmium oleate as zinc salt or cadmium salt, sulphur powder as sulphur source, and tri octyl phosphine is complex, is dissolved in octadecylene, and CuInS is added dropwise under 210 °C2In nano-particle solution, CuInS is obtained2/ ZnS core-shell nanos or CuInS2/ CdS core-shell nanos, its highest quantum yield respectively reaches 67% or 86% (Liang Li, et al., JACS, 2011,133 (5), 1176-1179).The content of the invention
According to one embodiment of present invention, a kind of method for preparing core-shell nanoparticle solution provided by the present invention, comprises the following steps：
A) semi-conductor nano particles solution is adjusted to a presetting shell and wraps up temperature；B) a shell precursor solution is added in the semi-conductor nano particles solution, and reacted at a temperature of the presetting shell parcel, the shell precursor solution is mixed to form by the composition including zinc salt, protective embankment base mercaptan and non-polar organic solvent；
C) after the reaction carries out the presetting reaction time, the core-shell nanoparticle solution of the semi-conductor nano particles is obtained；
The semiconductor preferably is selected from following one kind：Ι Β-Ι Π Α-VIA compounds of group or IIB-IB-IIIA-VIA compounds of group.
Ι Β-Ι Π Α-Group VIA the compound, IB preferably is selected from following one or more： Cu、 Ag;Ι Π Α preferably are selected from following one or more： In、 Ga;VIA preferably is selected from following one or more： Se、 S.
Ι Β-Ι Π Α-Group VIA the compound is more preferably from following one kind： CuInS2、 AgInS2、
CuInSe2、 AgInSe2、 CuGaS2、 CuGaSe2、 AgGaS2、 AgGaSe2, CuInGaS, CuAgInS, CuInGaSe, CuAgInSe, AgInGaS, AgInGaSe, CuAgGaS, CuAgGaSe, CuInSeS, AglnSeS or CuAgGaSeS.
The IB-IIIA-VIA compounds of group is most preferably from following one kind： CuInS2、 AgInS2、 CuInSe2、 AgInSe2、 CuGaS2, CuInGaS, CuAglnS or AglnGaS.
The IIB-IB-IIIA-VIA compounds of group, IB preferably is selected from following one kind or many clocks： Cu、 Ag;Ι Π Α preferably are selected from following one or more： In、 Ga;VIA preferably is selected from following one or more： Se、 S;Π Β races are selected from Zn.
The IIB-IB-IIIA-VIA compounds of group is more preferably from following one kind： ZnCuInS2、 ZnAgInS2、 ZnCuInSe2、 ZnAgInSe2、 ZnCuGaS2、 ZnCuGaSe2、 ZnAgGaS2、 ZnAgGaSe2, ZnCuInGaS, ZnCuAglnS, ZnCuInGaSe, ZnCuAglnSe, ZnAglnGaS, ZnAglnGaSe, ZnCuAgGaS, ZnCuAgGaSe, ZnCuInSeS, ZnAglnSeS or ZnCuAgGaSeSo
The IIB-IB-IIIA-VIA compounds of group is most preferably from following one kind： ZnCuInS2、 ZnAgInS2、 ZnCuInSe2、 ZnAgInSe2Or ZnAglnSeS.
Described add includes directly pouring into or being added dropwise dropwise.
The shell precursor solution is until formed by zinc salt dissolving as the mixing of zinc salt, alkyl hydrosulfide and non-polar organic solvent, heating.
Other organic coordination compounds are optionally added in the shell precursor solution preparation process.The organic coordination compound is selected from following one or more：Phosphate and aliphatic amine.
The molar content of the protective embankment base mercaptan is more than zinc salt molar content.
The mol ratio of the alkyl hydrosulfide and zinc salt is preferably (2 80):1, more preferably（2~50) ：1, be most preferably（4~20) ： 1. The zinc salt is selected from following one or more：Zinc acetate, zinc chloride, zinc sulfate, zinc diethyl dithiocarbamate, dihexyl zinc dithiocarbamate, zinc stearate, zinc oleate, Zinc tetradecanoate, zinc palmitate, zinc laurate and capric acid zinc.
The protective embankment base mercaptan is selected from the mercaptan with one or more than one mercapto functional group.
The protective embankment base mercaptan preferably is selected from following one or more：Octyl mercaptan, iso-octyl mercaptan, 12 protective embankment base mercaptan, 14 protective embankment base mercaptan, 16 protective embankment base mercaptan, Stearyl mercaptan, 1,8- dioctyls mercaptan and 1,6- dioctyl mercaptan.
The non-polar organic solvent is selected from following one or more：Octadecylene, dodecane, 16 protective embankments, 18 protective embankments, 3,5-dimethylphenyl ether, hydrogenated terphenyl, paraffin, diphenyl ether, dioctyl ether and two Bian ethers.
The phosphate is selected from following one or more：The pungent fat of tricresyl phosphate and tributyl phosphate.The aliphatic amine preferably is selected from following one or more：Cetylamine, octadecylamine, tetradecy lamine and oleyl amine.
The mol ratio of the zinc salt and phosphate is 1:(1：80), preferably 1:(2：50), more preferably 1:(4： 20).
The zinc salt is 1 with aliphatic mol ratio:(1：80), preferably 1:(2：50), more preferably 1:(4： 20).
The shell parcel temperature is 150 °C 290 °C, preferably 200 °C ~ 260 °C, more preferably 220 °C 250 °C.
The reaction time is lmir！4h, preferably 5min 3h, more preferably 15min 2h.According to another embodiment of the invention, a kind of method for preparing core-shell nano provided by the present invention, comprises the following steps：
Core-shell nanoparticle solution prepared by any one above-mentioned method is mixed to form suspension with a polar solvent；Separate the suspension and obtain the core-shell nano.
Further comprise step：The isolated core-shell nano is cleaned at least one times, to go the removal of impurity.
The polar solvent is selected from following one or more：Methanol, ethanol, isopropanol, butanol, MEK and acetone.
The core component of the core-shell nano is according to the different and different of selected semi-conductor nano particles.The shell component of the core-shell nano is ZnS.Accordingly, prepared core-shell nano can be expressed as semi-conductor nano particles/ZnS, for example, AgInS2/ZnS、
AgCuInS2/ZnS、 ZnCuInS2/ ZnS and ZnAgInS2/ ZnS etc..The core component surface of core-shell nano can be wrapped up partly or entirely by shell component.
The core-shell nano that the present invention is prepared can be applied in fields such as light emitting diode, solar cell, laser, electronic communication, anti-counterfeiting technology, biomarkers.
In the present invention, protective embankment base mercaptan chelates to form zinc organic compound, improves dissolubility of the zinc salt in non-polar organic solvent in zinc salt course of dissolution on the one hand as organic coordination compound with zinc salt.On the other hand, protective embankment base mercaptan also serves as sulphur source, slow decompose discharges sulphur at a temperature of shell parcel, and uniformly generate ZnS on semi-conductor nano particles surface with above-mentioned zinc organic compound, so as to reduce the defect of semi-conductor nano particles plane of crystal, the fluorescence quantum yield of core-shell nano is improved.Further, the slow decomposition of alkyl hydrosulfide effectively prevent the independent nucleation of ZnS, reduce the generation of accessory substance, further increase the fluorescence quantum yield of core-shell nano.
The present invention has the characteristics that compared with prior art：
1. the alkyl hydrosulfide that the present invention is used reduces the defect of semi-conductor nano particles plane of crystal, also reduce the generation of accessory substance, so as to improve the fluorescence quantum yield of core-shell nano, the fluorescence quantum yield of obtained core-shell nano can reach 75%.
2. raw material and reagent that the present invention is used are cheap, be readily obtained, nontoxic or low toxicity, production cost are low.
3. the present invention using protective embankment base mercaptan as sulphur source and organic coordination compound, simplify raw material type, can using directly pour into technique process simplification, process be easily controlled, repeatability it is good, it is easy to industrialize.Brief description of the drawings
The C that Fig. 1 embodiments in accordance with the present invention are obtainedUInS2The ultraviolet-visible absorption spectroscopy of/ZnS core core/shell nanoparticles. The CuI that Fig. 2 embodiments in accordance with the present invention are obtainednS2The C that Ying Guang Guang And Fig. 3 of/ZnS core-shell nanos are prepared according to one embodiment of present inventionUInS2The transmission electron microscope photo of/ZnS core core/shell nanoparticles.
The CuInS that Fig. 4 are prepared according to one embodiment of present invention2Nano-particle and CuInS2The X-ray diffractogram of/ZnS core core/shell nanoparticles.
The CuInS that Fig. 5 are prepared according to one embodiment of present invention2The transmission electron microscope photo of nano-particle.
Listed accompanying drawing is used to further describe the specific embodiment and method using disclosure of the invention, and accompanying drawing and the description are illustrative and not restrictive.Embodiment
With reference to specific embodiment, the present invention is expanded on further.It should be understood that these embodiments are only illustrative of the invention and is not intended to limit the scope of the invention.In addition, it is to be understood that after the content of the invention lectured has been read, those skilled in the art can make various changes or modifications to the present invention, these equivalent form of values equally fall within the application appended claims limited range.
Semi-conductor nano particles solution is adjusted to presetting shell and wraps up temperature, shell precursor solution is added into（For example can directly it pour into）Reacted into the semi-conductor nano particles solution, and at a temperature of presetting shell parcel.Reaction was carried out after the presetting reaction time, obtained the core-shell nanoparticle solution of semi-conductor nano particles.The core-shell nanoparticle solution is cooled to below the shell parcel temperature, such as room temperature.Above-mentioned core-shell nanoparticle solution and a polar solvent are mixed to form suspension, above-mentioned suspension is separated and obtains core-shell nano.The mode that shell precursor solution is added in semi-conductor nano particles solution preferably can comparatively fast make the mode that both comparatively fast mix, for example, quickly pour into shell precursor solution in semi-conductor nano particles solution.
Semi-conductor nano particles can be isolated from the semi-conductor nano particles solution of preparation, it would however also be possible to employ other existing process are prepared.
For example：The semi-conductor nano particles solution can be prepared using following steps：One or more in metal salt, indium salts and protective embankment base mercaptan, nitric sulfid, sulphur powder, thiocarbamide, which are added to, nonpolar to be had In machine solvent, be passed through inert gas, be heated to while stirring 200 ° (290 °C, and at this temperature continue stir lm！6h, makes metal salt, indium salts and alkyl hydrosulfide dissolving, obtains semi-conductor nano particles solution.The temperature and time prepared in semi-conductor nano particles solution processes will influence the particle size of semi-conductor nano particles, and then influence the luminescent properties of core-shell nano.
In Ι Β-Π Ι Α-Group VIA compound semiconductor solution, the ratio of IB races metal salt total mole number and Π Ι Α races metal salt total mole number is 12：21, wherein IB races metal salt can be mixed with Π Ι Α races metal salts with arbitrary proportion；The molar content of Group VIA element is more than or equal to IB races and Ι Π Α races metal salt total mole number molar content.
In IIB-IB-IIIA-VIA compound semiconductor solution, the ratio 1 ~ 2 of IB races metal salt total mole number and Ι Π Α races metal salt total mole number：2-1, IB race metal salt can be mixed with Π Ι Α races metal salts with arbitrary proportion；The molar content of Group VIA compound is more than or equal to IB races and Π Ι Α races metal salt total mole number molar content, and the ratio of Π Β races metal salt total mole number and IB races and Group IIIA metal salt total moles is 1 ~ 20： 20〜1.
IB races metal salt is selected from following one or more：Cuprous acetate, copper acetate, copper chloride, stannous chloride, cuprous sulfate, cuprous nitrate, copper nitrate, cuprous iodide, stearic acid are cuprous, oleic acid is cuprous, myristic acid is cuprous, palmitic acid is cuprous, laurate is cuprous, capric acid is cuprous, silver nitrate, silver sulfate, silver acetate or silver stearate.
Described Ι Π Α races metal salt is selected from following one or more：Indium acetate, inidum chloride, indium sulfate, indium nitrate, indium iodide, stearic acid indium, oleic acid indium, myristic acid indium, palmitic acid indium, laurate indium, capric acid indium, gallium chloride, gallium sulfate, stearic acid gallium, acetic acid gallium or gallium nitrate.
The Π Β races metal salt is selected from following one or more：Zinc acetate, zinc chloride, zinc sulfate, zinc diethyl dithiocarbamate, dihexyl zinc dithiocarbamate, zinc stearate, zinc oleate, Zinc tetradecanoate, zinc palmitate, zinc laurate and capric acid zinc.
The Group VIA compound is selected from following one or more：Selenium powder, two（Trimethyl silicon substrate）Selenium.
The protective embankment base mercaptan preferably is selected from following one or more：Octyl mercaptan, iso-octyl mercaptan, 12 protective embankment base mercaptan, 14 protective embankment base mercaptan, 16 protective embankment base mercaptan, 18, baked bases mercaptan, 1,8- dioctyls mercaptan and 1,6- dioctyl mercaptan. The non-polar organic solvent is selected from following one or more：Octadecylene, 12 protective embankments, 16 protective embankments, 18 protective embankments, 3,5-dimethylphenyl ether, hydrogenated terphenyl, paraffin, diphenyl ether, dioctyl ether and two Bian ethers.
The semi-conductor nano particles solution, it would however also be possible to employ semi-conductor nano particles are dispersed to organic solvent and obtained.
The organic solvent is selected from following one or more：Octadecylene, dodecane, hexadecane, octadecane, 3,5-dimethylphenyl ether, hydrogenated terphenyl, paraffin, diphenyl ether, dioctyl ether and, Bian ether, the mercaptan with one or more than one mercapto functional group, the pungent fat of tricresyl phosphate, tributyl phosphate, cetylamine, octadecylamine, tetradecy lamine and oleyl amine.
The experimental method of unreceipted actual conditions in the following example, generally according to normal condition, such as catalyst chemical operation manual, or according to the condition proposed by manufacturer.
The characterizing method of core-shell nano is as follows：
1) ultraviolet-visible absorption spectroscopy and fluorescence spectrum
To the core-shell nano of acquisition with carrying out optical performance test after dilution with toluene.The absorption spectrum of visible spectrophotometer test sample is foretold using UV-50 (Varian, USA) purple sunset, fluorescence spectrum test is carried out using Cary Eclipse (Varian, USA) types sepectrophotofluorometer to identical solution.When measuring fluorescence spectrum, PMT voltages are set to 600 V, and excitation wavelength is 485nm, and it is 5.0 nm to excite with transmite slit width.During to core-shell nano dilution with toluene, to make core-shell nano wavelength be 485nm at absorbance 0.05 or so, so as to avoid influence of the reabsorption of sample to follow-up data calculating process.
2) fluorescence quantum yield
With rhodamine B ethanol solution（Rhodamine B is in the fluorescence quantum yield that 97%) as standard test core-shell nano the quantum yield of ethanol solution is.The ethanol solution of rhodamine B and core-shell nano are tuned into unanimously in the absorbance of excitation wave strong point during test, and control 0.05 or so to avoid the reabsorption of sample.Fluorescence spectrum based on acquisition calculates the integral area of fluorescence peak, and passes through the fluorescence quantum yield of formula calculating core-shell nano. YQ is the quantum yield of core-shell nano to be measured,
YSFor standard dyes rhodamine B ethanol solution fluorescence quantum yield,
FQ, Fs be core-shell nano toluene solution to be measured, the integrated fluorescence intensities of rhodamine B ethanol solution,
Eight (3 and AsCore-shell nano toluene solution respectively to be measured and rhodamine B ethanol solution excitation wave strong point absorbance, and
0 (3 and 05Respectively it is used for the refraction coefficient for diluting the toluene solvant of core-shell nano and the alcohol solvent for diluting rhodamine B.
3) X-ray diffraction（XRD)
Core-shell nano toluene solution is dripped and forms film after on glass, drying naturally.Utilize X x ray diffractometer xs（Rigaku Co., Ltd., D/max-2200/PC) composition of core-shell nano is tested.Cu/ Κ-α are used for radiographic source, operating voltage is 40 KV, electric current is 30 mA, and scanning range is 20-70 °, and sweep speed is 6 min.
4) transmission electron microscope（TEM)
Copper mesh is impregnated in the core-shell nano toluene solution after cleaning, used after natural air drying
The type Flied emission transmission electron microscopes of TEM, Philips CM 20 obtain the transmission electron microscope photo of sample.Embodiment 1:Shell wraps up the time to CuInS2/ ZnS core core/shell nanoparticles performance impact mixing 0.293g zinc acetates, 3ml lauryl mercaptans and 6ml octadecylene solvents.100 °C are heated the mixture to until zinc salt dissolving, forms shell precursor solution.
By 0.051g cuprous acetates, 0.120g indium acetates and 1.03ml lauryl mercaptans are added in 10.3ml octadecylene solvents, and in a nitrogen atmosphere after stirring degassing 30min, certain time is stirred under 240 °C（It is shown in Table 1), forms CuInS2Nano-particle solution.
Shell precursor solution is quickly poured into CuInS2Nano-particle solution, the presetting reaction time is reacted at a temperature of 240 °C of shell parcel（After being shown in Table 1), obtain containing CuInS2The solution of/ZnS core core/shell nanoparticles, and it is cooled to room temperature.
Addition contains CuInS2The acetone and isopropyl alcohol mixture of 3 times of volumes of solution of/ZnS core core/shell nanoparticles（Acetone is 4 with isopropanol volume ratio:1) suspension is formed, by centrifugal sedimentation of suspension, The upper solution after centrifugal sedimentation is removed, C is obtainedUInS2/ ZnS core core/shell nanoparticles sediment.
Sediment is dispersed in toluene, the acetone and isopropyl alcohol mixture of 3 times of volumes of toluene is then added（Acetone is 4 with isopropanol volume ratio:1) cleaned, then centrifugal sedimentation, repeat said process 2 times.Obtained CUInS2/ ZnS core core/shell nanoparticles are dispersed in toluene, are stored in a nitrogen atmosphere.Table 1 is CUInS2/ ZnS core core/shell nanoparticles preparation condition and its performance.Fig. 1 and Fig. 2 are core-shell nano sample Yl, Y3, Y5, Y6, Y8-10 respectively, and sample Y16 ultraviolet-visible absorption spectroscopy and fluorescence spectrum.Fig. 3 is core-shell nano sample Y7 transmission electron microscope photo.
Table 1: CuInS2/ ZnS core core/shell nanoparticles preparation condition and its Xing Warehouse I
Experiment shows, by controlling to prepare CUInS2In the reaction time of mixing time and progress encapsulation reaction during nano-particle solution, CuInS can be adjusted2The fluorescence spectrum wavelength of/ZnS core core/shell nanoparticles, obtains the luminous of different colours.By optimization of process conditions, the orange-colored light that fluorescence spectrum wavelength is 589nm can be obtained, its fluorescence quantum yield can reach 75%.Embodiment 2:Zinc salt consumption is to CuInS2/ ZnS core core/shell nanoparticles performance impact Mix a certain amount of zinc acetate（Be shown in Table 2), 3ml lauryl mercaptans and 6ml octadecylene solvents.100 °C are heated the mixture to until zinc salt dissolving, forms shell precursor solution.
By 0.036g cuprous acetates, 0.084g indium acetates and 0.72ml lauryl mercaptans are added in 7.20ml octadecylene solvents, and in a nitrogen atmosphere after stirring degassing 30min, 60min is stirred under 240 °C, CuInS ft rice corpuscles solution is formed, and is cooled to 220 °C.
Shell precursor aqueous solution is quickly poured into CuInS^ft rice corpuscles solution, the presetting reaction time is reacted under 220 °C（After being shown in Table 2), obtain containing CuInS2The solution of/ZnS core core/shell nanoparticles, and it is cooled to room temperature.
Addition is containing CuInS2The acetone and isopropyl alcohol mixture of 3 times of volumes of solution of/ZnS core core/shell nanoparticles（Acetone is 4 with isopropanol volume ratio:1) suspension is formed, by centrifugal sedimentation of suspension, the upper solution after centrifugal sedimentation is removed, obtains CUInS2/ ZnS core core/shell nanoparticles sediment.
Sediment is dispersed in toluene, addition is that (acetone and isopropanol volume ratio are 4 for the acetone and isopropyl alcohol mixture of 3 times of volumes of toluene:1) cleaned, then centrifugal sedimentation, repeat said process 2 times.By obtained CUInS2/ ZnS core core/shell nanoparticles are dispersed in toluene, are stored in a nitrogen atmosphere.Table 2 is CuInS2/ ZnS core core/shell nanoparticles preparation condition and its performance.Fig. 4 is core-shell nano sample Yl l, Y13 and Υ 5 XRD spectrum.Fig. 5 is core-shell nano sample Yl 1 transmission electron microscope photo.
Table 2: CuInS2/ ZnS core core/shell nanoparticles preparation condition and its property Hui I
Embodiment 3:Whipping temp is to CuInS2/ ZnS core core/shell nanoparticles performance impact mixing 0.440g zinc acetates, 3ml 1- DDM dodecyl mercaptans and 6ml octadecylene solvents.100 °C are heated the mixture to until zinc salt dissolving, forms shell precursor solution.
By 0.075g cuprous acetates, 0.175g indium acetates and 1.50ml lauryl mercaptans are added in 15.00ml octadecylene solvents, in a nitrogen atmosphere after stirring degassing 30min, 30min is stirred under 260 °C, CuInS is formed2Nano-particle solution, and it is cooled to 240 °C.
Shell precursor solution is quickly poured into CuInS2Nano-particle solution, reacts the presetting reaction time under 240 °C（After being shown in Table 3), obtain containing CuInS2The solution of/ZnS core core/shell nanoparticles, is cooled to room temperature.
Addition is containing CuInS2The acetone and isopropyl alcohol mixture of 3 times of volumes of solution of/ZnS core core/shell nanoparticles（Acetone is 4 with isopropanol volume ratio:1) suspension is formed, by centrifugal sedimentation of suspension, the upper solution after centrifugal sedimentation is removed, obtains CuInS2/ ZnS core core/shell nanoparticles sediment.
Sediment is dispersed in toluene, addition is that (acetone and isopropanol volume ratio are 4 for the acetone and isopropyl alcohol mixture of 3 times of volumes of toluene:1) cleaned, then centrifugal sedimentation, repeat said process 2 times.By obtained CUInS2/ ZnS core core/shell nanoparticles are dispersed in toluene, are stored in a nitrogen atmosphere.Table 3 is CUInS2/ ZnS core core/shell nanoparticles preparation condition and its performance.
Table 3: CuInS2/ ZnS core core/shell nanoparticles preparation condition and its property are agreed
Embodiment 4:Non-polar organic solvent changes to CUInS2/ ZnS core core/shell nanoparticles performance shadow mixing 0.440g zinc acetates, 3ml lauryl mercaptans and 6ml octadecylene solvents.By mixture 100 °C are heated to until zinc salt dissolving, forms shell precursor solution.
By 0.074g cuprous acetates, 0.175g indium acetates and 1.50ml lauryl mercaptans are added in 15ml xylyl ethers, in a nitrogen atmosphere after stirring degassing 30min, 60min is stirred under 240 °C, CuInS is formed2Nano-particle solution, and it is cooled to 220 °C.
Shell precursor solution is quickly poured into CuInS2Nano-particle solution, reacts under 220 °C
After 180min, obtain containing CuInS2The solution of/ZnS core core/shell nanoparticles, and it is cooled to room temperature.
Addition is containing CUInS2The acetone and isopropyl alcohol mixture of 3 times of volumes of solution of/ZnS core core/shell nanoparticles（Acetone is 4 with isopropanol volume ratio:1) suspension is formed, by centrifugal sedimentation of suspension, the upper solution after centrifugal sedimentation is removed, obtains CuInS2/ ZnS core core/shell nanoparticles sediment.
Sediment is dispersed in toluene, addition is the acetone and isopropyl alcohol mixture of 3 times of volumes of toluene
(acetone and isopropanol volume ratio are 4:1) cleaned, then centrifugal sedimentation, repeat said process 2 times.By obtained CUInS2/ ZnS core core/shell nanoparticles are dispersed in toluene, are stored in a nitrogen atmosphere.The C of formationUInS2The fluorescence quantum yield of/ZnS core core/shell nanoparticles is 53.0%, and fluorescence spectrum wavelength is 587nm.Embodiment 5:Zinc precursor changes to CUInS2/ ZnS core core/shell nanoparticles performance impact
Mix 0.8662g zinc diethyl dithiocarbamates, 3ml lauryl mercaptans and 6ml octadecylene solvents.100 °C are heated the mixture to until zinc salt dissolving, forms shell precursor solution.
By 0.074g cuprous acetates, 0.175g indium acetates and 1.50ml 1- DDM dodecyl mercaptans are added in 15ml xylyl ethers, in a nitrogen atmosphere after stirring degassing 30min, 60min is stirred under 240 °C, CuInS is formed2Nano-particle solution, and it is cooled to 220 °C.
Shell precursor solution is quickly poured into CuInS2Nano-particle solution, reacts after 120min under 220 °C, obtains containing CuInS2The solution of/ZnS core core/shell nanoparticles, and it is cooled to room temperature.
Addition is containing CUInS2The acetone and isopropyl alcohol mixture of 4 times of volumes of solution of/ZnS core core/shell nanoparticles（Acetone is 4 with isopropanol volume ratio:1) suspension is formed, by centrifugal sedimentation of suspension, the upper solution after centrifugal sedimentation is removed, obtains CUInS2/ ZnS core core/shell nanoparticles sediment.
Sediment is dispersed in toluene, addition is that (acetone and isopropanol volume ratio are 4 for the acetone and isopropyl alcohol mixture of 3 times of volumes of toluene:1) cleaned, then centrifugal sedimentation, repeat said process 2 It is secondary.By obtained CuInS2/ZnS core-shell nanos are dispersed in toluene, are stored in a nitrogen atmosphere.The CuInS of formation2The fluorescence quantum yield of/ZnS core core/shell nanoparticles is 53.7%, and fluorescence spectrum wavelength is 605nm.Embodiment 6:Organic coordination compound oleyl amine is to CUInS2/ ZnS core core/shell nanoparticles performance impact mixing 0.2205g zinc acetates, 3ml lauryl mercaptans, 3ml oleyl amines and 6ml octadecylene solvents.Heating the mixture to 10, (TC is until zinc salt dissolving, forms shell precursor solution.
By 0.074g cuprous acetates, 0.175g indium acetates and 1.50ml 1- DDM dodecyl mercaptans are added in 15ml xylyl ethers, in a nitrogen atmosphere after stirring degassing 30min, 60min is stirred under 240 °C, CuInS^fi rice corpuscles solution is formed.
Shell precursor solution is quickly poured into CuInS2Nano-particle solution, reacts after 60min under 240 °C, obtains containing CuInS2The solution of/ZnS core core/shell nanoparticles, and it is cooled to room temperature.
Addition is containing CuInS2The acetone and isopropyl alcohol mixture of 4 times of volumes of solution of/ZnS core core/shell nanoparticles（Acetone is 4 with isopropanol volume ratio:1) suspension is formed, by centrifugal sedimentation of suspension, the upper solution after centrifugal sedimentation is removed, obtains CuInS2/ ZnS core core/shell nanoparticles sediment.
Sediment is dispersed in toluene, addition is that (acetone and isopropanol volume ratio are 4 for the acetone and isopropyl alcohol mixture of 3 times of volumes of toluene:1) cleaned, then centrifugal sedimentation, repeat said process 2 times.By obtained CUInS2/ ZnS core core/shell nanoparticles are dispersed in toluene, are stored in a nitrogen atmosphere.The CuInS of formation2The fluorescence quantum yield of/ZnS core core/shell nanoparticles is 20.9%, and fluorescence spectrum wavelength is 576nm.Embodiment 7:Organic coordination compound octadecylamine is to CUInS2/ ZnS core core/shell nanoparticles performance impact mixing 0.2205g zinc acetates, 3ml lauryl mercaptans, 3ml octadecylamines and 6ml octadecylene solvents.100 °C are heated the mixture to until zinc salt dissolving, forms shell precursor solution.
By 0.074g cuprous acetates, 0.175g indium acetates and 1.50ml 1- DDM dodecyl mercaptans are added in 15ml xylyl ethers, in a nitrogen atmosphere after stirring degassing 30min, 60min is stirred under 240 °C, CuInS is formed2Nano-particle solution.
Shell precursor solution is quickly poured into CuInS2Nano-particle solution, reacts under 240 °C After 60min, obtain containing CuInS2The solution of/ZnS core core/shell nanoparticles, and it is cooled to room temperature.Addition is containing CuInS2The acetone and isopropyl alcohol mixture of 4 times of volumes of solution of/ZnS core core/shell nanoparticles（Acetone is 4 with isopropanol volume ratio:1) suspension is formed, by centrifugal sedimentation of suspension, the upper solution after centrifugal sedimentation is removed, obtains CUInS2/ ZnS core core/shell nanoparticles sediment.
Sediment is dispersed in toluene, addition is the acetone and isopropyl alcohol mixture of 3 times of volumes of toluene
(acetone and isopropanol volume ratio are 4:1) cleaned, then centrifugal sedimentation, repeat said process 2 times.By obtained CUInS2/ ZnS core core/shell nanoparticles are dispersed in toluene, are stored in a nitrogen atmosphere.The C of formationUInS2The fluorescence quantum yield of/ZnS core core/shell nanoparticles is 42%, and fluorescence spectrum wavelength is 582nm.Embodiment 8:Organic coordination compound trioctyl phosphate is to CUInS2/ZnS core-shell nanos performance impact mixing 0.2205g zinc acetates, 3ml lauryl mercaptans, 5ml trioctyl phosphates and 3ml octadecylene solvents.100 °C are heated the mixture to until zinc salt dissolving, forms shell precursor solution.
By 0.074g cuprous acetates, 0.175g indium acetates and 1.50ml 1- DDM dodecyl mercaptans are added in 15ml xylyl ethers, in a nitrogen atmosphere after stirring degassing 30min, are stirred 60min at 230 times, are formed CuInS ^ rice corpuscles solution.
Shell precursor solution is quickly poured into CuInS2Nano-particle solution, reacts after 60min under 230 °C, obtains containing CuInS2The solution of/ZnS core core/shell nanoparticles, and it is cooled to room temperature.
Addition is containing nucleocapsid CuInS2The acetone and isopropyl alcohol mixture of 4 times of volumes of solution of/ZnS nano-particles（Acetone is 4 with isopropanol volume ratio:1) suspension is formed, by centrifugal sedimentation of suspension, the upper solution after centrifugal sedimentation is removed, obtains CuInS2/ ZnS core core/shell nanoparticles sediment.
Sediment is dispersed in toluene, addition is the acetone and isopropyl alcohol mixture of 3 times of volumes of toluene（Acetone and isopropanol volume ratio are 4:1) cleaned, then centrifugal sedimentation, repeat said process 2 times.By obtained CUInS2/ ZnS core core/shell nanoparticles are dispersed in toluene, are stored in a nitrogen atmosphere.The CuInS of formation2/ZnThe fluorescence quantum yield of S core-shell nanos is 38%, and fluorescence spectrum wavelength is 594nm. Embodiment 9: AgInS2The synthesis of/ZnS core core/shell nanoparticles
Mix 0.220g zinc acetates, 3ml lauryl mercaptans and 6ml octadecylene solvents.100 °C are heated the mixture to until zinc salt dissolving, forms shell precursor solution.
By 0.085g silver nitrates, 0.175g indium acetates and 1.5ml lauryl mercaptans are added in 15ml octadecylene solvents, in a nitrogen atmosphere after stirring degassing 30min, 15min is stirred under 240 °C, AgInS is formed2Nano-particle solution.
Shell precursor solution is quickly poured into AgInS2Nano-particle solution, reacts after 60min under 220 °C, obtains containing AgInS2The solution of/ZnS core core/shell nanoparticles, and it is cooled to room temperature.
Addition is containing AgInS2The acetone and isopropyl alcohol mixture of 4 times of volumes of solution of/ZnS core core/shell nanoparticles（Acetone is 4 with isopropanol volume ratio:1) suspension is formed, by centrifugal sedimentation of suspension, the upper solution after centrifugal sedimentation is removed, obtains AgInS2/ ZnS core core/shell nanoparticles sediment.
Sediment is dispersed in toluene, addition is that (acetone and isopropanol volume ratio are 4 for the acetone and isopropyl alcohol mixture of 3 times of volumes of toluene:1) cleaned, then centrifugal sedimentation, repeat said process 2 times.By obtained AgInS2/ ZnS core core/shell nanoparticles are dispersed in toluene, are stored in a nitrogen atmosphere.Embodiment 10: ZnCuInS2The synthesis of/ZnS core core/shell nanoparticles
Mix 0.220g zinc acetates, 3ml lauryl mercaptans and 6ml octadecylene solvents.100 °C are heated the mixture to until zinc salt dissolving, forms shell precursor solution.
By 0.076g cuprous acetates, 0.175g indium acetates, 0.109g zinc acetates and 1.5ml lauryl mercaptans are added in 15ml octadecylene solvents, in a nitrogen atmosphere after stirring degassing 30min, 90min is stirred under 230 °C, ZnCuInS is formed2Nano-particle solution.
Shell precursor solution is quickly poured into ZnCuInS2Nano-particle solution, after 220 times are reacted 60min, is obtained containing ZnCuInS2The solution of/ZnS core core/shell nanoparticles, and it is cooled to room temperature.
Addition is containing ZnCuInS2The acetone and isopropyl alcohol mixture of 4 times of volumes of solution of/ZnS core core/shell nanoparticles（Acetone is 4 with isopropanol volume ratio:1) suspension is formed, by centrifugal sedimentation of suspension, the upper solution after centrifugal sedimentation is removed, obtains ZnCuInS2/ ZnS core core/shell nanoparticles sediment. Sediment is dispersed in toluene, addition is the acetone and isopropyl alcohol mixture of 3 times of volumes of toluene（Acetone is 4 with isopropanol volume ratio:1) cleaned, then centrifugal sedimentation, repeat said process 2 times.By obtained CUInS2/ ZnS core core/shell nanoparticles are dispersed in toluene, are stored in a nitrogen atmosphere.Embodiment 11: CuInS2The synthesis of/ZnS core core/shell nanoparticles
Mix 0.293g zinc acetates, 3ml lauryl mercaptans and 6ml octadecylene solvents.100 °C are heated the mixture to until zinc salt dissolving, forms shell precursor solution.
By 0.051g cuprous acetates, 0.120g indium acetates and 1.03ml lauryl mercaptans are added in 10.3ml octadecylene solvents, and in a nitrogen atmosphere after stirring degassing 30min, 60min is stirred under 240 °C, room temperature is cooled to, adding 33ml acetone makes CuInS2Nano-particle solution centrifugal sedimentation, removes the upper solution after centrifugal sedimentation, obtains CuInS2Nano-particle.
By 0111^2Nano-particle is dispersed in 5ml toluene, and the acetone for adding 20ml is cleaned, then centrifugal sedimentation, repeats said process 2 times.By obtained CuInS2Nano-particle is dispersed in 11ml octadecylene, in a nitrogen atmosphere after stirring degassing 30min, is rapidly heated to 240 °C, is quickly poured into after shell precursor solution, heating stirring 60min, obtains CuInS2The solution of/ZnS core core/shell nanoparticles, and it is cooled to room temperature.
Addition is containing CUInS2The acetone and isopropyl alcohol mixture of 4 times of volumes of solution of/ZnS core core/shell nanoparticles（Acetone is 4 with isopropanol volume ratio:1) suspension is formed, by centrifugal sedimentation of suspension, the upper solution after centrifugal sedimentation is removed, obtains CUInS2/ ZnS core core/shell nanoparticles sediment.
Sediment is dispersed in toluene, addition is the acetone and isopropyl alcohol mixture of 3 times of volumes of toluene（Acetone is 4 with isopropanol volume ratio:1) cleaned, then centrifugal sedimentation, repeat said process 2 times.Obtained CuInS ZnS core core/shell nanoparticles are dispersed in toluene, stored in a nitrogen atmosphere.The CuInS of formation2The fluorescence quantum yield of/ZnS core core/shell nanoparticles is 70%, and fluorescence spectrum wavelength is 561nm.

Claims (13)

  1. Claims
    1. a kind of method for preparing core-shell nanoparticle solution, comprises the following steps：
    A) semi-conductor nano particles solution is adjusted to a presetting shell and wraps up temperature；B) a shell precursor solution is added in the semi-conductor nano particles solution, and reacted at a temperature of the presetting shell parcel, the shell precursor solution is mixed to form by the composition including zinc salt, alkyl hydrosulfide and non-polar organic solvent；
    C) after the reaction carries out the presetting reaction time, the core-shell nanoparticle solution of the semi-conductor nano particles is obtained；
    2. preparation method as claimed in claim 1, wherein, the molar content of the alkyl hydrosulfide is more than zinc salt molar content.
    3. preparation method as claimed in claim 1 or 2, wherein, the mol ratio of the protective embankment base mercaptan and zinc salt is (2 80)： 1.
    4. preparation method as claimed in claim 1, wherein, the protective embankment base mercaptan is selected from the mercaptan with one or more than one mercapto functional group.
    5. preparation method as claimed in claim 4, wherein, the alkyl hydrosulfide is selected from following one or more：Octyl mercaptan, iso-octyl mercaptan, lauryl mercaptan, tetradecyl mercaptan, 16 protective embankment base mercaptan, 18 protective embankment base mercaptan, 1,8- dioctyls mercaptan and 1,6- dioctyl mercaptan.
    6. the preparation method as described in claim 1,2 or 4, wherein, the non-polar organic solvent is selected from following one or more：Octadecylene, dodecane, 16 protective embankments, 18 protective embankments, 3,5-dimethylphenyl ether, hydrogenated terphenyl, paraffin, diphenyl ether, dioctyl ether and two Bian ethers.
    7. the preparation method as described in claim 1,2 or 4, wherein, the shell parcel temperature be 150 °C 290 ° (：.
    8. preparation method as claimed in claim 7, wherein, the shell parcel temperature is 260 °C of 200T.
    9. the preparation method as described in claim 1,2 or 4, wherein, the reaction time is lmii！〜 4h.
    10. preparation method as claimed in claim 9, wherein, the reaction time is 15min~2h。
    A kind of 1 1. methods for preparing core-shell nano, comprise the following steps：
    Core-shell nanoparticle solution prepared by any one method in claim 1- 10 is mixed to form suspension with a polar solvent；
    Separate the suspension and obtain the core-shell nano.
    12. the preparation method as described in claim 11, further comprises step：The isolated core-shell nano is cleaned at least one times, to go the removal of impurity.
    13. the preparation method as described in claim 11 or 12, wherein, the polar solvent is selected from following one or more：Methanol, ethanol, isopropanol, butanol, MEK and acetone.
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